Ring-opening polymerization of emulsion-templated deep eutectic system monomer for macroporous polyesters with controlled degradability†

Biodegradable polyesters with interconnected macroporosity, such as poly(L-lactide) (PLLA) and poly(ε-caprolactone) (PCL), have gained significant importance in the fields of tissue engineering and separation. This study introduces functional macroinitiators, specifically polycaprolactone triol (PCL_T) and polyethylene glycol (PEG), both OH-terminated, in the solventless ring-opening polymerization (ROP) of a liquid deep eutectic system monomer (DESm) composed of LLA and CL at a 30 : 70 molar ratio, respectively. The macroinitiators selectively initiate the organocatalyzed ROP of LLA in the DESm during the first polymerization stage, thereby modifying the PLLA architecture. This results in the formation of either branched or linear PLLA copolymers depending on the macroinitiator, PCL_T and PEG, respectively. In the second stage, the ROP of the CL, which is a counterpart of the DESm, produces PCL that blends with the previously formed PLLA. The insights gained into the PLLA architectures during the first stage of the DESm ROP, along with the overall molecular weight and hydrophobicity of the resulting PLLA/PCL blend in bulk, were advantageously used to design polymerizable high internal phase emulsions (HIPEs) oil-in-DESm. By incorporating a liquid mixture of DESm and macroinitiators (PCL_T or PEG), stable HIPE formulations were achieved. These emulsions sustained the efficient organocatalyzed ROP of the continuous phase at 37 °C with high conversions. The resulting polymer replicas of the HIPEs, characterized by macroporous and interconnected structures, were subjected to a degradation assay in PBS at pH 7.4 and 37 °C and remained mechanically stable for at least 30 days. Notably, they exhibited the capability to sorb crude oil in a proof-of-concept test, with a rate of 2 g g⁻¹. The macroporous and interconnected features of the polyHIPEs, combined with their inherent degradation properties, position them as promising degradable polymeric sorbents for efficient separation of hydrophobic fluids from water.